Fluorinated oxyvinyl compounds and methods of preparing and using same

ABSTRACT

Fluorine containing oxyvinyl compounds characterized by having one or more oxyvinyl groups separated from fluorine containing groups by at least one alkylene group having 2-8 carbon atoms and by at least one oxygen atom in addition to the oxygen on the oxyvinyl. In general the compounds of the invention have the generic formula: 
     
         Rz(L).sub.a (Ry).sub.b OROCH═CH.sub.2. 
    
     Where L is ═CHCOOROCH═CH 2  ; a is number of 0 to about 1; R y  is --CO--; b is a number of 0 to about 1; R is cycloalkane or (CH 2 ) x  --, where x is a number of about 2 through about 10; R z  is R f  C n  H m  where R f  is a fluorinated alkylene moiety of about 1 to about 12 carbon atoms which may be linear or branch chained and may contain a further --OROCH═CH 2  group; n is an integer of about 1 through about 6; and m is an integer of n to 2n. The compounds are suitable for use in optical devices such as fibers and waveguides, are readily radiation curable and curable by other means, and can be formulated to be of low viscosity when applied. The compounds are also suited for coatings, inks and adhesive and other applications. The invention includes methods for preparing and using the compounds and products employing the compounds. Intermediates to prepare the compounds and methods to prepare the intermediates are also included.

BACKGROUND OF THE INVENTION

This invention relates to vinyl ethers which are extremely reactivemonomers, known to undergo polymerization either by a cationic or a freeradical mechanism and are useful in applications which require a highspeed curing of a resin formulation. Vinyl ethers react much faster thanthe epoxy resins and therefore may be used for such applications asprinting inks, coatings, elastomers, foams and other types of productsdependent upon the ability of the resin to cure at a rate which isconsistent with other processing steps.

This invention relates to fluorinated vinyl ethers and more particularlyrelates to such fluorinated compounds containing one or more oxyvinylgroups. "Oxyvinyl group" as used herein means a vinyl group connected tothe remainder of the compound through an ether oxygen atom.

Some fluorinated chemical compounds are known in the art which containoxyvinyl groups such as are described in U.S. Pat. No. 2,732,370 underthe generic formula C_(n) F_(2n+1) CH₂ --O--CH═CH₂. The compoundsF--(CF₂)₃ --CH₂ ----O--CH═CH₂ and F--(CF₂)₃ ----O--CH═CH₂ arecommercially available from the company "Monomer-Polymer & Dajac". Theforegoing known compounds have fluorinated structures near the oxyvinylgroup and are thus believed either not to be radiation curable or not tohave radiation curable reactivities to the extent desired. Further, dueto the heavily fluorinated structure, adherence to substrates andcompatibility with solvents and cosolutes may not be as good as desired.

Continuing development of a new coatings has led to the need forimproving performance in certain applications. Such improvements caninclude control of flexibility, hardness, moisture resistance, and lowsurface energy.

One known methodology used to modify the properties of coating materialsis to employ nonionic fluorochemical surfactants. These surfactants havebeen shown to achieve lower surface tension. It is also known to thoseskilled in the art, that the use of additives which are not inherentlybonded in the matrix of the resin can result in decreased performance asa function of time due to migration or removal as a natural consequenceof abrasion or handling. There is therefore a need for a chemicallybonded material which can impart novel characteristics to resins,without loss of activity, and which is chemically miscible with thecomponents of a matrix under investigation.

The use of photocuring technology has grown rapidly within the lastdecade. Photocuring involves the radiation induced polymerization orcrosslinking of monomers into a three dimensional network. Photocuringhas a number of advantages including: a 100% conversion to a solidcomposition, short cycle times and limited space and capitalrequirements.

Photocuring technology has been applied in planar waveguideapplications. See, B. M. Monroe and W. K. Smothers, in Polymers forLightwave and Integrated Optics, Technology and Applications, L. A.Hornak, ed., p. 145, Dekker, 1992. In its simplest application, aphotocurable composition is applied to a substrate and irradiated withlight in a predetermined pattern to produce (the light transmissive) orwaveguide portion on the substrate. Photocuring permits one to recordfine patterns (<1 μm) directly with light. The refractive indexdifference between the substrate and the light transmissive portion ofthe substrate can be controlled by either regulating the photocurablecomposition or the developing conditions.

Because of the dramatic growth in the telecommunications industry thereis a need to develop photocurable compositions for optical waveguide andinterconnect applications. In order to be useful in these applications,the photocurable composition must be highly transparent at the workingwavelength and possess low intrinsic absorption and scattering loss.Unfortunately, in the near-infrared region, among which the 1300 and the1550 nm wavelengths are preferred for optical communications,conventional photocurable materials possess neither the requiredtransparency or low intrinsic absorption loss.

The absorption loss in the near-infrared stems from the high harmonicsof bond vibrations of the C--H bonds which comprise the basic moleculesin conventional acrylate photopolymers. One way to shift the absorptionbands to higher wavelengths, is to replace most, if not all, of thehydrogen atoms in the conventional materials with heavier elements suchas deuterium, fluorine, and chlorine; e.g. as described by T. Kaino, inPolymers for Lightwave and Integrated Optics, Technology andApplications, L. A. Homak, ed., p. 1, Dekker, 1992. The replacement ofhydrogen atoms with fluorine atoms is the easiest of these methods. Itis known in the art that optical loss at 1300 and 1550 nm can besignificantly reduced by increasing the fluorine to hydrogen ratio inthe polymer. It has been reported that some perfluorinated polyimidepolymers have very low absorption over the wavelengths used in opticalcommunications. See, S. Ando, T. Matsuda, and 5. Sasaki, Chemtech,1994-12, p. 20. Unfortunately, these materials are not photocurable.

U.S. Pat. No. 5,274,174 discloses a new class of photocurablecompositions comprised of certain fluorinated monomers, such asdiacrylates with perfluoro or perfluoropolyether chains, which possesslow intrinsic absorption loss. It is, therefore, possible to make lowloss optical interconnects from a photocurable system including thesematerials.

Fluorine substitution in the polymer structure, however, also inducessome other less desirable changes in the polymer's physical properties.One such change is the decrease in refractive index. For a highlyfluorinated acrylate photopolymer, the refractive index decreases to the1.32 region when the H/F mole ratio reaches 0.25. For opticalinterconnect applications, to avoid loss of light, it is important thatthe refractive index of the core of a planar waveguide approximate andpreferably match that of the optical fiber (generally 1.45). Anotherproblem with fluorine substitution in the polymer is the decrease of thesurface energy of the resulting photopolymer film which results in itsreduced adhesion to other materials such as found in substrates.

It is also important to be able to precisely control and fine tune therefractive index of the photopolymer at the working wavelength inoptical waveguide and interconnect applications. A desired index ofrefraction can be produced by mixing photocurable monomers withdifferent refractive indices. Most photopolymers made from conventionalphotocurable monomers have refractive indices in the region of1.45-1.55. Depending on the application, it is often desirable to lowera photopolymer's refractive index. One way to do this is to mix lowrefractive index fluorinated monomers with conventionalhydrocarbon-based monomers. Unfortunately, this is difficult toaccomplish because of the incompatibility or insolubility of thedifferent monomer systems. Thus, there is a need for photocurablecompositions which: (I) possess low optical loss in the near-infraredregion, (II) possess a refractive index approaching traditional opticalfibers; and (III) are compatible with both conventionalhydrocarbon-based and highly fluorinated monomers.

BRIEF DESCRIPTION OF THE INVENTION

In accordance with the present invention, novel fluorine containingcompounds are therefore provided which are suitable for use in opticaldevices such as fibers and waveguides. These novel compounds are readilyradiation curable and curable by other means. These compounds aresoluble with other components (cosolutes) and in numerous recoverableand re-useable solvents, and can be formulated to be of low viscositywhen applied.

The novel fluorine containing compounds provide enhanced surfaceproperties, and are fast curing but have indefinite pot life beforeexposure to radiation or other curing processes. The compounds, whencured, have a low refractive index. The compounds have good substrateadhesion, and can be chemically bonded into other resins, eliminatingmigratory problems associated with materials which are not bonded into aformulation, In addition, the compounds can be made from commerciallyavailable materials by both known and novel processes.

The compounds of the present invention are characterized by having oneor more oxyvinyl groups separated from fluorine containing groups by atleast one alkylene group having 1-8 carbon atoms and by at least oneoxygen atom in addition to the oxygen on the oxyvinyl structure. Morespecifically, the compounds of the invention are oxyvinyl monoethers,oxyvinyl diethers, oxyvinyl monoesters and oxyvinyl diesters of fluorinecontaining structures.

In general the compounds of the invention have the generic formula:

    R.sub.z (L).sub.a (Ry).sub.b OROCH═CH.sub.2.

Where L is ═CHCOOROCH═CH₂ ; a is number of 0 to about 1; R_(y) is--CO--; b is a number of 0 to about 1; R is cycloalkane or (CH₂)_(x) --,where x is a number of about 2 through about 10; R_(z) is R_(f) C_(n)H_(m) where R_(f) is a fluorinated alkylene moiety of about 1 to about12 carbon atoms which may be linear or branch chained and may contain afurther --OROCH═CH₂ group; n is an integer of about 1 through about 6;and m is an integer of n to 2n.

Fluorinated oxyvinyl monoethers of the invention may be characterized bythe above generic formula where a and b are 0 and R_(z) is free ofadditional oxyvinyl ether groups. The oxyvinyl monoethers may thus berepresented by the formula:

    R.sub.f C.sub.n H.sub.m OROCH═CH.sub.2.

Fluorinated oxyvinyl diethers of the invention may be characterized bythe above generic formula where a is 0, b is 0, and R_(z) containsanother --OROCH═CH₂ group. The oxyvinyl diethers may thus be representedby the formula:

    R.sub.f C.sub.n H.sub.m [OROCH═CH.sub.2 ].sub.2,

Fluorinated oxyvinyl monoesters of the invention may be characterized bythe above generic formula where R_(y) is --CO--, b is 1, and a is 0. Theoxyvinyl monoesters may thus be represented by the formula:

    R.sub.f C.sub.n H.sub.m COOROCH═CH.sub.2.

Fluorinated oxyvinyl diesters of the invention may be characterized bythe above generic formula where a is 1 and b is 1. The oxyvinyl diestersmay thus be represented by the formula:

    R.sub.f C.sub.n H.sub.m CH[COOROCH═CH.sub.2 ].sub.2

The invention further includes novel methods of making the abovecompounds and uses of such compounds in coatings, inks, adhesives,structural polymers optical devices including fiber optics and waveguides, and to make photocured products using photocuring processes.

The invention further includes a novel method for making the fluorinatedester intermediates R_(f) C_(n) H_(m) CH[COOR]₂, used in making thefluorinated oxyvinyl monoesters and diesters of the invention., whereR_(f), C_(n), H_(m) and R are as previously described. R is preferablylower alkyl of about 1 to about 4 carbon atoms, e.g. methyl, ethyl,propyl, and butyl. The method comprises using a reaction solvent whichis a mixture of tetrahydofuran (THF) and n-methylpyrrolidinone (NMP).

The invention also includes the novel intermediate R₁ SO₃ (R)CH═CH₂,used in making the fluorinated oxyvinyl monoethers and diethers of theinvention, where R₁ can be alkyl, aryl or alkylaryl such as methyl,phenyl, or tolyl, where R₁ contains from about 1 to about 10 carbonatoms and R is as defined above.

DETAILED DESCRIPTION OF THE INVENTION

R_(f) as used herein may be perfluorinated or partially fluorinated andmay be linear or branch chained. R_(f), in addition to containinghydrogen and fluorine, may contain other substitutions, such as anoxyvinyl ether group, as previously discussed. The R_(f) group mayadditionally contain other halogen substitutions, especially chlorine orbromine, e.g. R_(f) may be CX₃ --(CF₂)_(c) --, where X is chlorine orbromine and c is about 1 to about 11. R_(f) may also include one or morehydroxy, ether, ester, nitro, thio, mercapto, sulfo, heterocyclo,phenyl, substituted phenyl, cycloalkyl or substituted cycloalkyl groups.Specific examples of possible R_(f) substituents are --OH, , --COOCH₃,--OCH₃, --OCH₂ CH₃, NO₂, --SH, --SCH₃, phenyl, benzyl, cyclohexyl, andchlorocyclohexyl. In most cases, with the exception of halogen, theabove substituents are attached to a non-fluorinated carbon atom of theR_(f) group. Such substituents may also be attached to a C_(n) or Rcarbon atom, provided that the substituent is not so electrophylic thatit interferes with the stability of the oxyvinyl group. For that reason,the C_(n) and R carbon atoms generally do not contain the highlyelectrophylic fluorine substituent.

The R group, as previously discussed, in addition to normal alkyl, maybe branch chain, (still intended to be encompassed by the --(CH₂)_(x) --structural formula since the total number of carbon and hydrogen atomsremains constant whether the structure is linear or branched). The Rgroup may also be cycloalkane, meaning that R may be cycloalkane aloneor in conjunction with normal or branched alkane, e.g. cyclohexylmethyl.

The compounds of the invention may be made by a number of methods whichform part of the present invention.

For example the fluorinated oxyvinyl ethers of the invention may be madeby reacting an alkoxide of a fluorinated alcohol with a sulfonate vinylether of the formula R₁ SO₃ (R)OCH═CH₂ where R₁ and R are as definedabove. The fluorinated alcohol may be either a monofunctional alcohol ora diol. When a monofunctional alcohol is reacted with one mole of thesulfonate vinyl ether, a mono functional fluorinated oxyvinyl ether isobtained. When a diol is reacted with two moles of the sulfonate vinylether, a fluorinated oxyvinyl diether is obtained.

Many suitable monofunctional alcohols may be defined by the formulaR_(f) '(CF₂)_(x) C_(n) H_(m) OH, where R_(f) ' is --CF₃, --CHF₂, --CH₂F, or --CH₃ and x, n, and m are as previously defined. Specific examplesof suitable commercially available fluorinated alcohols are:

1H,1H,8H,8H-dodecafluoro-1,8-octanediol, [HOCH₂ (CF₂)₆ CH_(2OH];)

2,2,3,3,4,4-hexafluoro-1,5-pentanediol, [HOCH₂ (CF₂)₃ CH₂ OH];

2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, [HOCH₂ (CF₂)₄ CH₂ OH];

1H,1H,10H,10H-hexadecafluoro-1,10-decanediol, [HOCH₂ (CF₂)₈ CH₂ OH];

1H,1H,12H,12H-icosafluoro-1,12-dodecanediol, [HOCH₂ (CF₂)₁₀ CH₂ OH];

octafluoropentanol, [HCF₂ CF₂ CF₂ CF₂ CH₂ OH];

2,2,2trifluoroethanol, [CF₃ CH₂ OH]; and

1H,1H,7H-dodecafluoro-1-heptanol, [CHF₂ (CF₂)₅ CH₂ OH].

The reaction to form the fluorinated oxyvinyl ethers of the inventioninvolves reacting the alkoxide of a fluorinated alcohol with the novelsulfonate alkyl vinylethers. The fluorinated alcohol alkoxides areprepared by reacting the alcohol with a base sufficiently strong toselectively deprotonate only the hydroxyl proton. Bases suitable forthis reaction are the alkoxide bases of the alkali earth metals,preferably sodium or potassium, with the most preferred being sodiumt-butoxide. Additionally, bases such as the alkali earth hydrides canalso be employed with the most preferred being sodium hydride.

The novel sulfonate vinyl ethers for reaction with the fluorinatedalkoxide may be described by the formula:

    R.sub.1 SO.sub.3 (R)OCH═CH.sub.2

and may be prepared by reacting commercially available hydroxyvinylethers with a base sufficiently strong to produce the alkoxyalkylvinylether, followed by subsequent reaction with an alkyl or arylsulfonylchloride at a temperature conducive to result in the formation of thedesired sulfonate vinyl ether intermediate.

The bases required for effecting the transformation to thealkoxyalkylvinyl ether can be the same as defined for the production ofthe fluorinated alcohol alkoxides, described above. Sodium t-butoxideand sodium hydride are the preferred bases. The most preferred base issodium hydride.

The formation of either the fluorinated alcohol alkoxide or of thealkoxyalkylvinyl ether is performed at temperatures from -10 to 70° C.,with the most preferred temperature being 10-20° C. In addition, tofacilitate formation and dissolution, an inert solvent can be employedin the reaction. An inert solvent that can typically be used in thesynthesis is tetrahydrofuran.

To prepare the sulfonate alkylvinyl ether it is necessary to perform thereaction at sufficiently low temperatures to avoid decomposition orundesired side reactions. Temperatures suitable for this synthesis rangefrom -60 to 0° C. with the most preferred being -25 to -20° C. Thereaction is performed by adding the alkyl or azyl sulfonyl chloride tothe cooled preformed base of the alkoxyalkylvinyl ether solution.Typically, benzenesulfonyl chloride, toluenesulfonyl chloride ormethanesulfonyl chloride can be used.

Once the alkylvinyl ether sulfonate has been formed it is rapidly addedto the preformed fluorinated alcohol alkoxide solution. Formation of thedesired fluorinated oxyvinyl ether is accomplished by heating thereaction mixture to between 70-80° C. for a period of time sufficient tocomplete the reaction, as determined by analyzing the reaction mixtureby gas chromatography. This is normally achieved after 4-8 hours atreflux. Any reaction solvent that was utilized during the course of thereaction is removed by evaporation by conventional techniques followedby dissolving the remaining salts with water. The fluorinated oxyvinylether product separates from the water as a distinct phase and isisolated. Further purification of the product is accomplished by vacuumdistillation.

    __________________________________________________________________________    Specific examples of fluorinated oxyvinyl ethers of the invention              are:                                                                         __________________________________________________________________________    HCF.sub.2 (CF.sub.2).sub.3 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;       CF.sub.3 (CF.sub.2).sub.2 CH.sub.2 O(CH.sub.2).sub.2 OCH═CH.sub.2 ;       CF.sub.3 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;                        HCF.sub.2 (CF.sub.2).sub.5 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;      HCF.sub.2 (CF.sub.2).sub.3 CH.sub.2 O(CH.sub.2).sub.2 OCH═CH.sub.2 ;      CF.sub.3 CH.sub.2 O(CH.sub.2).sub.2 OCH═CH.sub.2 ;                        CCl.sub.3 CH.sub.2 O(CH.sub.2).sub.2 OCH═CH.sub.2 ;                        -                                                                             #STR1##                                                                       - CH.sub.2 ═CHO(CH.sub.2).sub.4 OCH.sub.2 (CF.sub.2).sub.6 CH.sub.2     O(CH.sub.2).sub.4 OCH═CH.sub.2 ;                                           CH.sub.2 ═CHO(CH.sub.2).sub.2 OCH.sub.2 (CF.sub.2).sub.6 CH.sub.2        O(CH.sub.2).sub.2 OCH═CH.sub.2 ;                                             -                                                                            #STR2##                                                                        - HOCH.sub.2 (CF.sub.2).sub.6 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub    .2 ;                                                                           CH.sub.3 OCH.sub.2 (CF.sub.2).sub.6 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH    .sub.2 ;                                                                       CH.sub.3 CH.sub.2 COOCH.sub.2 (CF.sub.2).sub.6 CH.sub.2 O(CH.sub.2).sub.4     OCH═CH.sub.2;                                                             HSCH.sub.2 (CF.sub.2).sub.6 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2       ##STR3##                                                                     __________________________________________________________________________

    ______________________________________                                        Examples of the intermediate sulfonate vinyl ethers of the                      invention are:                                                              ______________________________________                                          #STR4##                                                                       #STR5##                                                                        -                                                                           ##STR6##                                                                     ______________________________________                                    

The oxyvinyl esters of the invention are prepared by reacting acarboxylic acid ester containing an active methylene group, e.g.dimethylesters of propanedioic acid, with a base which is sufficientlyreactive to deprotenate at least one of the hydrogens from the activatedmethylene group. An active methyl group is one which will deprotenate inthe presence of a strong base. The anion resulting from deprotenation isreacted with a suitable fluorine containing intermediate, e.g. ahalogenated fluoroalkyl iodide to form a fluorinated ester compoundwhich is then esterified with a hydroxyvinyl ether to form thefluorinated vinyl ether esters of the invention.

A diagram of a scheme to obtain fluorinated oxyvinyl esters of theinvention is as follows:

    ROOCCH.sub.2 COOR+base+R.sub.f C.sub.n H.sub.m X→R.sub.f C.sub.n H.sub.m CH[COOR].sub.2

    R.sub.f C.sub.n H.sub.m CH[COOR].sub.2 +HO--(CH.sub.2).sub.x --O--CH═CH.sub.2 →R.sub.f C.sub.n H.sub.m CH[COOROCH═CH.sub.2 ].sub.2

Where R, R_(f), n, and m are as previously defined and X is chlorine,bromine or iodine.

The method for making the intermediate fluorinated ester compound R_(f)C_(n) H_(m) CH[COOR]₂ is unique and forms part of the present invention.

More specifically, in a preferred embodiment, propanedioic aciddiesters, e.g. dimethyl and diethyl malonates, are reacted with a basewhich is sufficiently reactive to deprotonate at least one of thehydrogens from the activated methylene group. Typical of the basesenvisioned in this patent are the alkoxides of the alkali earth metals,preferably sodium or potassium, with the most preferred being sodiumt-butoxide.

Similarly, bases such as the alkali earth hydrides can also be employed,with the most preferred being sodium hydride.

The intermediate fluorinated esters are prepared by a modification ofthe procedure described by Smeltz et al. in U.S. Pat. No. 3,504,016. Inthat patent, the inventors describe a method for preparing fluorinatedesters employing butanol as the solvent and sodium metal as the base.During the course of the reaction, copious quantities of precipitateform, rendering processing difficult. In addition, the mixed alcoholsystem results in the formation of mixed esters of the products.

Replacing the solvent system of U.S. Pat. No. 3,504,016 with a mixedsolvent system consisting of tetrahydrofuran (THF) andn-methylpyrrolidinone (NMP) in approximately 80:20 weight percent,eliminates this problem. It is understood that this ratio may be varied,e.g. from about 60:40 to about 90:10 THF to NMP. Specifically, thesolution remains homogeneous throughout the anion formation step and nocross esterification is observed. Pure products are isolated.

In addition to this improvement, the acid work up step of U.S. Pat. No.3,504,016 can be eliminated. This is particularly advantageous as traceamounts of acid in this product would have disastrous affects in thetransesterification with the vinyl ether compounds. In particular, rapidcross polymerization would occur this preventing product formation.

Fluorinated ester compounds, used as intermediates to make thefluorinated oxyvinyl esters of the invention, are prepared by reactingthe above activated methyl group anion with a suitable fluorinecontaining starting material, usually a halogenated fluoroalkyl iodideof the general structure R_(f) C_(n) H_(m) X where R_(f) is afluorinated alkyl group, as previously described, ; n is an integer ofabout 1 through about 6; m is an integer of n to 2n and X is chlorine,bromine or iodine. While the iodide derivative is the most preferred dueto its rapid reactivity, the other halogen derivatives namely Cl and Brare also contemplated in this invention.

Halogens other than iodine may be especially desirable when chorofluorocompounds of the invention are made. As an example, a chlorofluorocompound of the invention can be made by the following scheme:

    F.sub.2 C═CClF+BrCl.sub.3 C→CCl.sub.3 (CF.sub.2 CFCl).sub.n Br

    CCl.sub.3 (CF.sub.2 CFCl).sub.n Br+CH.sub.2 ═CH.sub.2 →CCl.sub.3 (CF.sub.2 CFCl)nCH.sub.2 CH.sub.2 Br

This bromide can, for example, be substituted for the iodide asdescribed above and in examples 11-20.

Reaction temperatures are not critical but are preferably conducted atthe reflux temperature of tetrahydrofuran. The reactants employed inthis process are readily available from commercial sources and are wellknown to those skilled in the art. It should also be apparent that byselecting the suitable reactant a variety of fluorinated esters can beprepared. In addition to the pure esters, the ester derived from theoligomeric mixture of fluorinated telomer iodides, commercially known asZonyl TELB-L and sold by DuPont, can also be prepared. These fluorinatedesters are required for the preparation of the vinyl ether esters ofthis invention.

The fluorinated vinyl ether esters of this invention are prepared bytransesterifying the above fluorinated esters with a hydroxyvinyl etherof structure

    HO--(CH.sub.2).sub.x --O--CH═CH.sub.2

where x is about 2 to about 8 and encompasses methyl, ethyl and the likeand cycloalkanes such as 1,4 cyclohexylmethylvinyl ether.

In the preferred practice of this invention, the fluorinated ester andhydroxyvinyl ether are combined in a 1:3 mole ratio for diester ethersand about 1:1.5 for monoester ethers. While these ratios are notcritical and can be as low as 1:2 or greater than 1:3 for diester and aslow as 1:1 or greater than 1:1.5 for monoesters, the 1:3 and 1:1.5ratios provide for an effective reaction rate and high productivity ofproduct. The reaction is preferably carried out in the presence of acatalyst, preferably titanium isopropoxide. While the amount of catalystis not critical, effective reaction rates are achieved when the moleratio of catalyst to fluorinated ester is at least 1×10⁻³ to 1.

Similarly, the reaction temperature is not critical, but must beperformed at an elevated value as compared to room temperature. Thepreferred temperature range is from 90-120° C. Reaction pressures arepreferably maintained below atmospheric to assist in the rapid removalof methanol, a by product of this reaction. Preferably, the reactionpressure is maintained between 50 and 150 mmHg during the course of thereaction. The final products are isolated by conventional vacuumdistillation.

    ______________________________________                                        Examples of the oxyvinyl esters of the present invention are:                 ______________________________________                                        CF.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4      OCH═CH.sub.2 ].sub.2 ;                                                      CCl.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.    4 OCH═CH.sub.2 ].sub.2 ;                                                   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4     OCH═CH.sub.2 ].sub.2 ;                                                     CF.sub.3 (CF.sub.2).sub.7 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4     OCH═CH.sub.2 ].sub.2 ;                                                     CF.sub.3 (CF.sub.2).sub.e CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4     OCH═CH.sub.2 ].sub.2 ;                                                      -                                                                             #STR7##                                                                       - CF.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3          ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ];                                 CF.sub.3 (CF.sub.2).sub.7 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3            ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ];                                 CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3            ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ]; and                             CF.sub.3 (CF.sub.2).sub.e CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3            ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ], where e is a                    number of about 1 to about 12.                                              ______________________________________                                    

Examples of fluorinated ester intermediates used to prepare thefluorinated oxyvinyl esters of the invention are as follows:

CF₃ (CF₂)₅ CH₂ CH₂ CH[CO₂ CH₃ ]₂ ;

CF₃ (CF₂)₇ CH₂ CH₂ CH[CO₂ CH₃ ]₂ ;

CF₃ (CF₂)₉ CH₂ CH₂ CH[CO₂ CH₃ ]₂ ; and

CF₃ (CF₂)_(e) CH₂ CH₂ CH[CO₂ CH₃ ]₂

The vinyl monomers of the invention contain much less hydrogen thanconventional photocurable monomers such that their inherentcarbon-hydrogen bond absorption is greatly reduced. In addition, theintroduction of chlorine or bromine atoms into the molecule can offsetthe effect of fluorine on the refractive index of the monomer producinga material with an index of refraction between about 1.40-1.48. As aresult, the monomers of the invention may be particularly useful inoptical applications in the 1300-1550 nm wavelength region. The monomersare also compatible with both conventional hydrocarbon-based and highlyfluorinated monomers. Because of this compatibility, it becomes possibleto fine tune the refractive index and other physical properties ofphotocurable compositions containing these photocurable monomer.

The invention thus includes a photocurable composition comprising atleast one photocurable monomer of the invention and a photoinitiator.

The invention also includes a process for producing an optical devicecontaining a light transmissive region comprising: (a) applying a filmof a photocurable composition comprising a photocurable monomer of theinvention and a photoinitiator to a substrate; (b) imagewise exposingsaid composition to sufficient actinic radiation to form exposed andunexposed areas on the substrate; and (c) removing the unexposedportions of the composition.

In still another embodiment, the invention includes an optical devicecomprising a light transmissive region wherein said light transmissiveregion comprises a photocurable composition of the invention. Suchoptical devices include waveguides, splitters, routers, couplers,combiners, optical fibers and parts and combinations of such devices.

Such optical devices can be made by molding methods as described, forexample, in U.S. Pat. No. 5,511,142. They can also be made by creatingregions with differing degrees of polymerization and, as a consequence,different refractive indexes as described, for example, in U.S. Pat. No.5,054,872. They can also be made through any combination of thesemethods or by other methods familiar to those skilled in the art ofmaking optical devices.

The compounds of the invention are characterized by unique and usefulproperties, including excellent surface wetting, low surface tension,low friction and high slip, low flammability, high temperatureresistance, low temperature resistance, low dielectric constant,nonstick surface characteristics, high chemical resistance, andexcellent moisture resistance.

In addition to optical applications, the compounds of the invention findutility in numerous other areas, including, but not limited to,coatings, inks, moldings, photoresists, films, fibers, adhesives,insulators, and laminates. The compounds of the invention may bepolymerized alone or with other vinyl or ethylenically unsaturatedmonomers, such as acrylates, other vinyl monomers and alkenes.

The following specific examples serve to illustrate and not limit thepresent invention. Unless otherwise indicated, all parts and percentagesare by weight.

EXAMPLE 1 Preparation of Butylvinyl Ether Benzenesulfonate

Into a 3 L flask equipped with a mechanical stirrer and N2 purge wasadded 1000 g of tetrahydrofuran and 220.7 g (2.3 mol) of sodiumt-butoxide. Hydroxybutyvinyl ether (236 g, 2.03 mol) was added dropwiseat a rate to maintain the temperature at ≦40° C. This reaction mass wascooled to -40° C. A solution of benzenesulfonyl chloride (353 g, 2 mol)in 300 g of tetrahydrofuran was added dropwise at a rate to maintain thereaction temperature at ≦-20° C. After the addition was complete, thereaction mixture was allowed to warm to room temperature to obtain thebutylvinyl ether benzenesulfonate, ##STR8##

EXAMPLE 2 Preparation of Ethylvinyl Ether Benzenesulfonate

This compound was prepared in a manner similar to that described inExample 1 except that ethylene glycol vinyl ether (178.9 g, 2.03 mol)was used in the synthesis. This compound has the structural formula:##STR9##

EXAMPE 3 Preparation of 1, 4-Cyclohexylmethylvinyl EtherBenzenesulfonate, ##STR10##

This compound was prepared in a manner similar to that described inExample 1 except that 1,4-cyclohexanedimethanol vinyl ether (398.5 g,2.03 mol) was used in the synthesis.

EXAMPLE 4 Preparation of 5H--Octafluoropentane-oxybutylvinyl Ether

HCF₂ (CF₂)₃ CH₂ O(CH₂)₄ OCH═CH₂

Octafluoropentanol (487.4 g, 2.1 mol) was added dropwise to a suspensionof sodium t-butoxide (203.8 g, 2.12 mol) in 500 g of tetrahydrofuran ata rate to maintain the reaction temperature at ≦25° C. After theaddition was complete, the reaction content produced in Example 1 wasadded and the reaction heated to 80° C. for 8 hours. The solvent wasthen removed by distillation and the resulting solid dissolved in 3 L ofwater. The lower organic phase was separated and the product distilledat 54-58° C./0.4 mm to yield 508.3 g (77%).

EXAMPLE 5 Preparation of Heptafluorobutane-oxyethylvinyl Ether

CF₃ (CF₂)₂ CH₂ O(CH₂)₂ OCH═CH₂

This material was prepared as described in Example 4 except that1H,1H-heptafluoro-1-butanol (424.1 g, 2.12 mol) and the reaction productfrom Experiment 2 was used. Yield of the product was 297.5 (82.5%).B.P.=77-80° C./50 mm.

EXAMPLE 6 Preparation of Trifluoroethyloxybutylvinyl Ether

CF₃ CH₂ O(CH₂)₄ OCH═CH₂

This material was prepared as described in Example 4 except that2,2,2-trifluoroethanol (900 g, 9 mol) was used. Yield of product whichwas distilled at 35-40° C./0.2 mm was 1488.11 g (84%).

EXAMPLE 7 Preparation of Dodecafluoroheptane-oxybutylvinyl Ether

HCF₂ (CF₂)₅ CH₂ O(CH₂)₄ OCH═CH₂

This compound was prepared as described in Example 4 except that1H,1H,7H-dodecafluoro-1-heptanol (704 g, 2.12 mol) was used in thereaction sequence. Yield of product was 729 g (80%). B.P.=67-70° C./0.1mm.

EXAMPLE 8 Preparation of 5H--Octafluoroventane-oxyethylvinyl Ether

HCF₂ (CF₂)₃ CH₂ O(CH₂)₂ OCH═CH₂

This compound was prepared as described in Example 4 except thealkoxyethyl vinyl ether prepared in Example 2 was used in the synthesis.Yield of product was 602 g (80%) based on a 2.5 mol scale.

The structure was confined by nmr and ir. B.P.=38-41° C./0.8-1 mm.

EXAMPLE 9 Preparation of Trifluoroethane-oxyethylvinyl Ether

CF₃ CH₂ O(CH₂)₂ OCH═CH₂

This compound was prepared as described in Example 6 except that thereagent prepared in Example 2 was used in the synthesis (0.25 molscale). Yield of product was 32 g (75%). B.P. --32-35° C./12 mm.

EXAMPLE 10 Preparation of Trifluoroethylcyclohexyl-dimethanol- monovinylEther, ##STR11##

This compound was prepared as described in Example 6 except that thereagent prepared in Example 3 was used in the synthesis. Yield of thereaction based on a 1 mol scale was 200 g (72%). B.P. --56-60° C./0.5mm.

EXAMPLE 11 Preparation of Propanedioic Acid,1H,1H,2H,2H-Perfluorooctane-dimethyl Ester

CF₃ (CF₂)₅ CH₂ CH₂ CH[CO₂ CH₃ ]₂

Sodium t-butoxide (22.1 g, 0.23 mol) was added to a solution of 120 mLof THF and 75 g of NMP. To this solution dimethylmalonate (27.77 g, 0.21mol) was added at a rate to maintain the internal temperature at <65° C.Stirring was continued at this temperature for 30 minutes followed bythe dropwise addition of 1-iodo-1H,1H,2H,2H-perfluorooctane (99.43 g,0.21 mol). After the addition was complete, the reaction mixture wasrefluxed at 75-80° C. for two hours. The reaction was determined to becomplete based on bas chromatograph analysis of the reaction mixture.The THF was removed at 120 mmHg/50° C. 150 mL of water was then added tothe remaining reaction mass. The product phase separated. The crudeproduct was distilled at 110-114° C./0.2 mmHg to yield 85 g (63% yield).

EXAMPLE 12 Preparation Propanedioic Acid, 1H,1H,2H,2H-Perfluorodecane-,Dimethyl Ester

CF₃ (CF₂)₇ CH₂ CH₂ CH[CO₂ CH₃ ]₂

This material was prepared as described in Example 11 except that1-iodo-1H,1H,2H,2H-perfluorodecane (99.3 g, 0.173 mo01) was substitutedas a raw material. The crude product was distilled at 110-114° C./0.2 mmto yield 74 g (74% yield).

EXAMPLE 13 Preparation of Propanedioic Acid,1H,1H,2H,2H-Perfluorododecane,-Dimethyl Ester

CF₃ (CF₂)₉ CH₂ CH₂ CH[CO₂ CH₃ ]₂

This material was prepared as in Example 11 except that1-iodo-1H,1H,2H,2H-perfluorododecane (250 g, 0.37 mol) was used as thestarting material. The crude product was distilled at 160-175° C./0.1 mmto yield 193.2 g (77% yield). The product solidified upon cooling.

EXAMPLE 14 Preparation Propanedioic Acid,1H,1H,2H,2H-α-Fluoropolydifluoromethylene,-Dimethyl Ester

CF₃ (CF₂)_(n) CH₂ CH₂ CH[CO₂ CH₃ ]₂ n=3,5,7,9 (mixture)

This material was prepared as described in Example 11 except that1-iodo-1H,1H,2H,2H-α-fluoropolydifluoromethylene (553 g, 1 mol) wassubstituted as a raw material. The crude product was distilled at150-160° C./0.2 mm to yield 445.6 g (80% yield).

EXAMPLE 15

Preparation of CF₃ (CF₂)_(n) CH₂ CH₂ CH[CO₂ CH₃ ]₂, using PropanedioicAcid, 1H,1H,2H,2H-α-Fluoropolydifluoro-methylene,--Dimethyl Ester withSodium Hydride as Base, n=3,5,7,9 (mixture)

The compound was prepared according to the procedure described inExample 11 except that NaH was substituted as base and the reaction wasrun on a 1 mol scale. Distillation afforded 420.7 g (76% yield).

EXAMPLE 16 Preparation of Propanedioic Acid,1H,1H,2H,2H-Perfluorooctane-,dibutyvinyl Ether Ester

CF₃ (CF₂)₅ CH₂ CH₂ CH[CO₂ (CH₂)₄ OCH═CH₂ ]₂

Propanedioic acid, 1H,1H,2H,2H-perfluorooctane--,dimethyl ester (85 g,0.178 mol), hydroxybutylvinyl ether (62 g, 0.53 mol) and titaniumtetraisopropoxide (0.081 g, 2.8×10⁻⁴ mol) were reacted at 110-112° C./50mm to effect the transesterification reaction. After three hours, theformation of the by product, methanol, was complete. The product wasisolated by vacuum distillation. The fraction boiling at 96-100° C./0.2mm was identified as the product fraction. Yield=131.5 g (97%).

EXAMPLE 17

CF₃ (CF₂)₉ CH₂ CH₂ CH[CO₂ (CH₂)₄ OCH═CH₂ ]₂

The propanedioic ester product produced in Example 13 (100 g, 0.15 mol)was reacted with hydroxybutylvinyl ether (51 g, 0.45 mol) and titaniumtetraisopropoxide (0.068 g, 2.4×10⁻⁴ mol) as described in Example 16.The product was isolated by distillation at 160° C./0.1 mm. Yield=111.7g (88%).

EXAMPLE 18

CF₃ (CF₂)₇ CH₂ CH₂ CH[CO₂ (CH₂)₄ OCH═CH₂ ]₂

The propanedioic ester from Example 12 (230 g, 0.398 mol) was reactedwith hydroxybutylvinyl ether (138.5 g, 1.19 mol) and titaniumtetraisopropoxide (0.181 g, 6.3×10⁻⁴ mol) as described in Example 16.The product was isolated by distillation at 140-145° C./0.2 mm.Yield=289 g (97%).

EXAMPLE 19

CF₃ (CF₂)_(n) CH₂ CH₂ CH[CO₂ (CH₂)₄ OCH═CH₂ ]₂, n=3,5,7,9 mixture

The propanedioic ester oligomer mixture produced in Example 15 (420 g,0.75 mol) was reacted with hydroxybutylvinyl ether (261 g, 2.25 mol) andtitanium tetraisopropoxide (0.342 g, 1.2×10⁻³ mol) as described inExample 16. The product was isolated by distillation at 110-160° C./0.1mm to yield 513.8 g (94%) of the bis(butylvinyl) ether fluorinatedmalonate.

EXAMPLE 20 ##STR12##

The propanedioic ester oligomer produced in Example 15 (385 g, 0.69 mol)was reacted with cyclohexanol monovinyl ether (353.1 g, 2 mol) andtitanium tetraisopropoxide (0.318 g, 1.11×10⁻³ mol) as described inExample 16. The product was isolated by distillation at 150-165° C./0.2mm to yield 514.8 g (90%). This example illustrates the use of a cyclicvinyl ether in the synthesis.

EXAMPLE 21

Acrylate and vinyl ether polymers were made by UV polymerization ofacrylate and vinyl ether monomers. Such polymers were prepared byhomopolymerization without additives, and with non-reactivefluorochemical surfactant additive and by copolymerization withcompounds of the present invention.

The resulting polymers were compared on the basis of surface fluorine,surface tension, blocking, release, bulk tensile properties andelongation.

The results are shown in the table.

Column 1 of the table gives the major resin composition in the polymerbeing tested.

The "acrylate" polymer comprised a cured mixture of 80 weight percentaliphatic urethane diacrylate oligomer, UCB Corporation trademark"Ehrecryl 8804"; 20 weight percent hexanediol diacrylate, and 2 partsper hundred (pph) of α α dimethoxy-phenylacetophenone, free radicalphotocuring initiator, available under Ciba Geigy trademark "Irgaccure651", plus additives shown in column 2 of the table.

The "acrylate" polymer was UV cured under nitrogen. At least about 200millijoules (mJ)/cm² of UV exposure from a medium pressure mercury lampwas required for complete cure.

"FAVE" means fluorochemical oxyvinyl ether of the invention.

FAVE alone was cured using sulfonium hexafluoroantimonatephotoinitiator, available from GE Corporation under the trademark GE-PI.Radiation exposure was about 400 mJ/cm² to cure.

"Vinyl Ether" in column 1 is a cured 50/50 combination of polyesterdivinyl ether oligomer, available from AlliedSignal, Inc. under thetrademark VEX 1221 and 1,2-benzene carboxylic acid bis [4-(ethenyloxy)butyl] ester, available from AlliedSignal, Inc. under the trademarkVE4010D. 0.5 pph of triaryl sulfonium salt of hexafluoro antimonatecationic photoinitiator was used. The photoinitiator is available fromSartomer Company, Inc. under the trademark CD1010. The vinyl ether wascompletely cured using about 400 mJ/cm² of UV radiation.

As shown in column 2 of the table, there was either no additive, FC430fluorochemical surfactant additive, FC171 fluorochemical surfactantadditive or a FAVE copolymerized additive of the invention. FC430 is atrademark of 3M Corporation for water soluble non-ionic fluoroaliphaticsurfactant. FC171 is a trademark of 3M Corporation for slightly watersoluble fluorochemical surfactant.

Column 3 of the table shows percent atomic fluorine at the top surface(TFS) by photoelectron spectroscopy based upon total carbon, nitrogen,oxygen, fluorine, and silicon.

Column 4 shows percent atomic fluorine at the bottom surface, (BFS).

Column 5 shows percent top surface atomic fluorine after 20+rubs withmethyl ethyl ketone (MEK) for the acrylate and 100% FAVE polymercoatings and 4+rubs with MEK for the vinyl ether polymer coatings.

Column 6 shows percent top surface atomic fluorine after being postcuredat 80° C. for 15 minutes and after 20+rubs with methyl ethyl ketone forpolyacrylate and 4+rubs for polyvinyl ether.

Column 7 shows surface tension in dynes/cm.

Column 8 shows block separation force between top surfaces using 44grams per square inch block forming pressure. Block separation force isforce in grams to peel back a blocked section of one half inch width at1.5 inches per minute.

Column 9 shows force of release of adhesive tape from the top surface at12 inches per minute. The tape used was 3M Corporation 810 adhesivetape.

Columns 10 and 11 show tensile strength using the Youngs Modulus in Ksi."Ksi"=1000 psi and stretch characteristics using percent elongation.

This example illustrates the resulting effect on surface energy byadding various load levels of the fluorinated oxyvinyl ethers of thisinvention into standard acrylate formulations and into standard vinylether formulations used by those in the industry. As can be seen, theaddition of the fluorinated vinyl ethers has a dramatic effect inreducing the surface tension in both the neat liquid and the cured filmat even the 0.1 wt % level. The lower surface tension in the liquidstate as compared to the patent formulation indicates that these fluidswill have an improved surface wetting property. Similarly, the decreasein surface energy of the polymerized film indicates that these materialswill exhibit low surface tension, low friction and non-stick surfaces.

This example further demonstrates the non-fugitive properties of thevinyl ethers of this invention in acrylate and vinyl ether polymercompositions. It compares the vinyl ethers of the invention tocommercially available fluorinated surfactants used in the art. As canbe observed, after performing the industry standard test of MEK doublerubs, polymerized films containing the fluorinated surfactant additivessignificantly decrease in percent surface content of fluorine ascompared to the fluorinated materials of this invention. Thissubstantiates the non-fugitive nature of the materials of the inventionas compared to current art materials, as well as demonstrating thatmaterials formulated and polymerized with the fluorinated ethers willexhibit extended wear performance, resistance and the like. The highersurface fluorine content of compounds of the invention, coupled with itssteady state value as compared to the decreasing value observed with thefluorinated surfactant series of fluorinated additives, demonstrateimprovements over prior art technology.

The results of this example further demonstrate that the oxyvinyl ethersof the invention can be used both in acrylate based polymers by freeradical polymerization and in vinyl ether based polymers by cationicpolymerization.

Materials of these compositions will impart improved wear, temperatureresistance and chemical resistance, just to indicate a few enhancedproperties. Such properties can thus be enhanced by use of the compoundsof the invention in many areas such as: coatings, plastics, inks,moldings, adhesives and optical devices.

                                      TABLE                                       __________________________________________________________________________    CORRELATION OF SURFACE FLUORINE WITH SURFACE TENSION, BLOCKING,                 RELEASE, BULK TENSILE PROPERTIES AND ELONGATION                                                           Surface               Tensile                       TFS BFS  TFS after Tension of Surface Top to Top  Youngs %                  Major  Atomic Atomic TFS after MEK Cured film Tension of Blocking                                                                    Release Modulus                                                               Elongation                                                                     Resin Additive                                                               Fluorine                                                                      Fluorine MEK                                                                  Postcure Top                                                                  Liquid Grams                                                                  Grams (Ksi) at                                                                Break                __________________________________________________________________________    Example 19                                                                          None  34.42                                                                             31.6                                                                              35.42                                                                              33.3                                                   FAVE                                                                          Acrylate None 0 0 0 0 42 51 5 626 56 31                                       100%                                                                          Acrylate 0.1 pph 8 0 6.1 7.1 32 46.9 2.6 611                                   Example 19                                                                    FAVE                                                                         Acrylate 0.5 pph 15.3 0.6 13.9 14 <30 42.2 1.4 350 54 31                       Example 19                                                                    FAVE                                                                         Acrylate 0.1 pph FC- 1.7 0.5 0.7 1.1 38 41.4 3.9 560                           430                                                                          Acrylate 0.5 pph FC- 6.7 0.69 1.8 5.5 36 35.5 2.5 465 51 34                    430                                                                          Acrylate 0.1 pph FC- 9.8 9.3 4.1 8.5 36 37.4 2.7 673                           171                                                                          Acrylate 0.5 pph FC- 15.6 11.4 10.9 16.9 34 32.6 1.4 675 47 29                 171                                                                          Acrylate 0.5 pph 9 0.3 7.5 7.9 30 40.2 2.3 493 45 40                           Example 16                                                                    FAVE                                                                         Acrylate 0.5 pph o.5 0.1 0.2 0.3 42 41.7 4.1 608 43 37                         Example 8                                                                     FAVE                                                                         Vinyl Ether None 0 0 0 0 744 36.6 345 611 115.7 30.3                          Vinyl Ether 0.5 pph FC- 9.83 1.47 2.67 3.36 34 30 2.3 388 153.2 14.3                                                                   430                  Vinyl Ether 0.5 pph FC- 12.95 1.12 1.59 4.6 34 29.3 3.2 604 141.2 22.2                                                                 171                  Vinyl Ether 0.5 pph 17.2 0.2 15.9 17.2 <30 36                                  Example 19                                                                    FAVE                                                                         Vinyl Ether 1.0 pph 21.74 0.54 20.2 20.81 <30 28 2.7 242 134.7 26.2                                                                    Example 19                                                                    FAVE                 Vinyl Ether 2.5 pph 25.65 1.23 24.63 25.31 <30 26.3 0.86 196 131.7 25.2        Example 19                                                                    FAVE                                                                         Vinyl Ether 5 pph 27.85 1.96 28.57 29.89 <30 25.2 1.0 160 136.8 24.4                                                                   Example 19                                                                    FAVE               __________________________________________________________________________

We claim:
 1. A compound having the formula:

    R.sub.z (L).sub.a (R.sub.y).sub.b OROCH═CH.sub.2

where L is ═CHCOOROCH═CH₂ ; a is 0 to about 1; R_(y) is --CO--; b is anumber of 0 to about 1; R is cycloalkane or (CH₂)_(x) --, where x is anumber of from about 2 to about 10; R_(z) is R_(f) C_(n) H_(m) whereR_(f) is a fluorinated alkylene moiety of from about 1 to about 12carbon atoms; n is an integer of from about 1 to about 6; and m is aninteger of from n to 2n provided that when R is CH₂ and a and b=0, x isat least 4 to about
 10. 2. The compound of claim 1 wherein R_(f) islinear chained.
 3. The compound of claim 1 wherein R_(f) of R_(z)further contains an --OROC═CH₂ group.
 4. The compound of claim 1 whereinR_(f) of R_(z) further contains at least one halogen selected from thegroup consisting of chlorine and bromine.
 5. The compound of claim 1wherein R_(f) of R_(z) further contains at least one group selected fromthe group consisting of --OH, --COOCH₃, --OCH₃, --OCH₂ CH₃, --NO₂, --SH,--SCH₃, phenyl, benzyl, cyclohexyl and chlorocyclohexyl.
 6. Afluorinated oxyvinyl monoether of claim 1 where a and b are
 0. 7. Afluorinated oxyvinyl diether of claim 1 where a is 0, b is 0, and R_(z)contains at least one --OROCH═CH₂ group.
 8. A fluorinated oxyvinylmonoester of claim 1 where b is 1, and a is
 0. 9. A fluorinated oxyvinyldiester of claim 1 where a is 1 and b is
 1. 10. An oxyvinyl etherselected from the group consisting of:

    __________________________________________________________________________    HCF.sub.2 (CF.sub.2).sub.3 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;       CF.sub.3 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;                        HCF.sub.2 (CF.sub.2).sub.5 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub.2 ;      CCl.sub.3 CH.sub.2 O(CH.sub.2).sub.2 OCH═CH.sub.2 ;                        -                                                                             #STR13##                                                                      - CH.sub.2 ═CHO(CH.sub.2).sub.4 OCH.sub.2 (CF.sub.2).sub.6 CH.sub.2     O(CH.sub.2).sub.4 OCH═CH.sub.2 ;                                           CH.sub.2 ═CHO(CH.sub.2).sub.2 OCH.sub.2 (CF.sub.2).sub.6 CH.sub.2        O(CH.sub.2).sub.2 OCH═CH.sub.2 ;                                             -                                                                            #STR14##                                                                       - HOCH.sub.2 (CF.sub.2).sub.6 CH.sub.2 O(CH.sub.2).sub.4 OCH═CH.sub    .2.                                                                           __________________________________________________________________________


11. A fluorinated oxyvinyl ester selected from the group consisting of:

    ______________________________________                                        CF.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4      OCH═CH.sub.2 ].sub.2 ;                                                      CCl.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.    4 OCH═CH.sub.2 ].sub.2 ;                                                   CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4     OCH═CH.sub.2 ].sub.2 ;                                                     CF.sub.3 (CF.sub.2).sub.7 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.4     OCH═CH.sub.2 ].sub.2 ;                                                     CF.sub.3 (CF.sub.2).sub.3-9 CH.sub.2 CH.sub.2 CH[CO.sub.2 (CH.sub.2).sub.    4 OCH═CH.sub.2 ].sub.2 ;                                                    -                                                                             #STR15##                                                                      - CF.sub.3 (CF.sub.2).sub.5 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3          ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ];                                 CF.sub.3 (CF.sub.2).sub.7 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3            ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ];                                 CF.sub.3 (CF.sub.2).sub.9 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3            ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ]; and                             CF.sub.3 (CF.sub.2).sub.3-9 CH.sub.2 CH.sub.2 CH[CO.sub.2 CH.sub.3          ][CO.sub.2 (CH.sub.2).sub.4 OCH═CH.sub.2 ].                               ______________________________________                                    


12. A method for preparing an oxyvinyl ether compound of claim 1comprising reacting an alkoxide of a fluorinated alcohol with asulfonate vinyl ether of the formula R₁ SO₃ (R)OCH═CH₂, where R₁ isalkyl of from about 1 to about 10 carbon atoms and R is cycloalkane or(CH₂)_(x) where x is from about 2 to about
 10. 13. The method of claim12 wherein the fluorinated alcohol has the formula R_(f) '(CF₂)_(x)C_(n) H_(m) OH, where R_(f) ' is --CF₃, --CHF₂, --CH₂ F, or --CH₃ and xis from about 2 to about 10, n is from about 1 to about 6, and m is anumber of from n to 2n.
 14. A method for th e preparation of afluorinated oxyvinyl ester compound according to claim 1 comprising:a)reacting a carboxylic acid containing an active methylene group with abase which is sufficiently reactive to deprotenate at least one of thehydrogens from the activated methylene group; b) reacting the resultinganion with a fluoroalkyl halide to form a fluorinated ester compound;and c) esterifying the fluorinated ester compound with a hydroxyvinylether to form the fluorinated oxyvinyl ester.
 15. The method of claim 14wherein the carboxylic acid containing an active methylene group has theformula ROOCCH₂ COOR.
 16. A method for the preparation of a fluorinatedester compound of the formula R_(f) C_(n) H_(m) CH[COOR] where R_(f) isa fluorinated alkylene moiety of from about 1 to about 12 carbon atomswhich may be linear or branch chained, n is a number of from about 2 toabout 6, m is a number of n to 2n, and R is cycloalkane or (CH₂)_(x)where x is about 2 to about 10; said method comprising:a) reacting acarboxylic acid ester of the formula ROOCCH₂ COOR containing an activemethylene group with a base which is sufficiently reactive todeprotenate at least one of the hydrogens from the activated methylenegroup; and b) reacting the resulting anion with a fluoroalkyl halide ofthe formula R_(f) C_(n) H_(m) X in a solvent comprising a mixture oftetrahydrofuran and n-methylpyrrolidinone to form the fluorinated estercompound.
 17. A fluorinated oxyvinyl diester of claim 1 where a is 1 andb is 0.